Methods of using particular carbamic acid esters for insecticidal and acaricidal purposes



United w Pmn Q ABSTRACT OF THE DISCLOSURE Method of killing insectsand/or acarids by applying to the corresponding insects, acarids and/orhabitat thereof a correspondingly effective amount of anN-(unsubstituted, alkyl, and alkoxyand/or halo-substituted alkyl)-N'-(alkyl, phenyl, and a1koxy-, halo-, nitroand/ or cyano-alkyl and-phenyl)-1-(1-fluoroacetamide-2,2,2-trichloro)-ethyl carbamate.

The present invention relates to new methodsof using particular carbamicacid esters for insecticidal and/or acaricidal purposes, either alone oras active ingredients in admixture with dispersible carrier vehicles.

These particular carbamic acid esters have been described and claimed incopending US. application Ser. No. 499,068, filed Oct. 20, 1965, whichstates that such esters have strong selective rodenticidal properties.-

12 Claims It is also known that 1-isopropyl-3-methyl-5 pyrazolyldimethylcarbamate (A) and a-naphthyl N-methyl carba mate (B) can be used asinsecticidally active .compounds. Theselast-mentioned twou compoundshave achieved considerable practical importance carbamate(B,)'can beused as an; acaricidally active c0mpound. This carbamate hasconsiderable importance for this purpose as well.

It is an object of the present invention to provide new methods of usingparticular carbamic acid esters for arthropodicidal, i.e., insecticidaland/or acaricidal, purposes, either alone or as active ingredients inadmixture with dispersible carrier vehicles. 7 1

Other and further objects of the present invention will become apparentfrom a study of thewithin specification and accompanying examples. L I

It has now been found, in accordance with the present invention, thatthe particular 1-(l-iiuoroacetamido-LZJQ trichloro)-ethyl carbamateshaving [the general formula 'j a R (I) in which R represents a memberselected from thegroup consisting of hydrogen, alkyl having l'4--carbonatoms, and substituted'alkyl having 1-4 carbon atoms which issubstituted with a member selected from the group con-' sisting ofalkoxy having 1-4 carbon atoms, halo, and

mixtures of such substituents, and R represents a member selected fromthe group consisting of alkyl having 1-4 carbon atoms, phenyl, and thecorresponding substituted alkyl and phenyl which are substituted with amember selected from thegroup consisting of alkoxy having "1+ carbonatoms, halo,"nitro, cyano, and mixtures of such substituents, havestrong arthropodicidal, i.e., insecticidal and acaricidal, properties.

It is very surprising that "the particular active compounds usableaccording to the present invention have a higher acaricidal andinsecticidal activity than the carbamates hitherto known for the samepurpose. The compositions according to the present invention thusconstitute a valuable addition to the art.

The particular carbamic acid esters of general Formula I can be obtainedby reacting in known. manner:

(a) Chloral-fluoroacetamide of the formula F-QHr-CONH-CHOH 0013 with anisocyanate of the general formula O=C=NR' in which R is the same asdefined above, or

(b) Chloral-fluoroacetamide (IIa') with a carbamic acid chloride of thegeneral formula (IIa) 6 O1--O--N V R (He) in which R and R' arethe sameas defined above.

The reaction according to (a) can be carried out in inert solvents.Hydrocarbons, such as benzine and benzene, or chlorinated hydrocarbons,especially methylene chloride, can be used for this purpose, as well asethers,"such as dioxan. The reaction is accelerated by the l addition ofa tertiary amine; for example, triethylamine. It is furthermore knownthata-naphthyl-N-methyl- The 'reaction temperatures ma be-v'a'riedwithin a fairly widerange. In general, the operation is carried outbetw'eentO and 100 C.

v The reaction according to (b) 'is expediently carried 1 out in thepresence of organic solvents, such as aromatic and aliphatichydrocarbons, and especially ethers, such as dioxan; or ketones, such asacetone-The liberated hydrochloric acid is expediently boundby organicor inorganic acid binding agents. Tertiary amines, such as diethylaniline-and pyridine, and alkalinietal hydroxides and alkalirnetalcarbonates may be usedfor this purpose. The acid binding agents areadded in equivalent amounts. The reaction "temperatures may be variedwithin a fairly wide range. They are preferably between 0 and 50 C.

. The'compounds usable according to the present invention surprisinglyhave a stronginse'cticidal and acaricidal activity but only a lowtoxicity to warm-blooded animals and "a low phytotoxicity. The effectsappear rapidly and are long-lasting. The compounds can, therefore, beused advantageously with good results for combating noxious sucking andbiting insects; Diptera and mites (Acarina)! Typical sucking insectscontemplated herein essentially include aphids, such-as the-peach aphid(Mycus persicae), the black bean aphid (Doralis, fabae), and the.

like; coccids, such as Aspidiotus heaerae, Lecanium hesperdiurm andPseudococcus maritz'mus, and the like;' :lfhysanoptera spchasIiercinqthrips femoralis, andthe like; and bugs, such as the beet-leafbug (Piesma quadrata), and the bed bug (Cimex lectularius), and thelike.

Also, typical biting insects contemplated herein essentially includebutterfly larvae, such as Plutella maculipenm's and Lymantria dispar,and the like; beetles, such as the grain weevil (Sitophz'lus granarius),the Colorado beetle (Leptinotarsa decemlineata), and also species livingin the soil, such as wire worms (Agriotes sp.) and cockchafer larvae(Melolontha melo lontha), and the like; cockroaches, such as the Germancockroach (Blatella germanica), and the like; Orthoptera, such as thecricket (Gryllus domesticus), and the like; termites, such asReticulitermes, and the like; and Hymenoptera, such as ants, and thelike.

Typical Diptcra contemplated herein essentially comprise the fiies, suchas the fruit fly (Drosophila melanogaster), the Mediterranean fruit fiy(Ceratitis capizata), the house fiy (Musca domestica), and gnats, suchas mosquito (Aedes aegypzi), and the like.

Among the typical mites contemplated herein, the spider mites(Tetranychidae) are of special importance, such as the common spidermite (T etranychus urticae), the fruit tree spider mite (Paratetranychuspilosus), and the like; gall mites, such as the red currant gall mite'(Eriophyes ribis) and tarsonemides, such as T arsonemus pallidus, andticks, and the like.

Thus, the particular compounds of the instant invention can be used asarthropodicides, i.e., insecticides and/ or acaricides, either alone orin admixture with solid or liquid carriers or diluents.

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withdispersible carrier vehicles, such as solutions, emulsions, suspensions,

' mixtures with one another ,substanceaif desired.

emulsifiable concentrates, spray powders, pastes, soluble powders,dusting agents, granulates, etc. These are prepared in known manner, forinstance by extending the active agents with dispersible liquid diluentcarriers and/ or dispersible solid carriers optionally with the use ofcarrier vehicle assistants including emulsifying agents and/ordispersing agents, whereby, for example, in the case where water is usedas diluent, organic solvents may be added as auxiliary solvents (cf.Agricultural Chemicals, March 1960, pages 3538). The following may bechiefly considered for use as carrier vehicles for this purpose:dispersible liquid diluent carriers, such as aromatic hydrocarbons (forinstance, benzene, toluene, xylene, etc.), halogenated, especiallychlorinated, aromatic hydrocarbons (for instance, chlorobenzenes),paraffins (for instance, petroleum fractions), chlorinated aliphatichydrocarbons (for instance, methylene chloride, etc.), alcohols (forinstance, methanol, ethanol, propanol, butanol, etc.), amines (forinstance, ethanolamine, etc.), amides (for instance, dimethyl formamide,etc.), ketones (for instance, acetone, etc.), and water; as well asdispersible finely divided solid carriers, such as natural groundminerals (for instance, kaolins, alumina, silica, chalk, i.e., calciumcarbonate, talc, kieselguhr, etc.) and synthetic ground minerals (forinstance, highly dispersed silicic acid, silicates, e.g., alkalisilicates, etc.); whereas the following may be chiefly considered foruse as carrier vehicle assistants for this purpose: emulsifying agents,such as non-ionic and anionic emulsifying agents (for instance,polyethylene oxide esters of fatty acids, polyethylene oxide ethersoffatty alcohols, alkyl sulfonates,-

aryl sulfonates, etc.,. and especially alkyl aryl-polyglycol ethers,magnesium stearate, sodium oleate, etc.); and

dispersing agents, such aslignin, sulfite waste liquors,

in such formulations orcompositions in the form of the artisan, theactive comand with other known active The substances according to theinvention may be employed by themselves as the artisan will appreciate,in the form of their compositions with solid or liquid dispersiblecarrier vehicles or other known compatible active agents, or in the formof particular dosage preparations for specific application madetherefrom, such as solutions, emulsions, suspensions, powders, pastes,and granulates which are thus ready for use.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about 01-95% by weight, andpreferably 05-90% by weight, of the mixture, wh'ereas carriercomposition mixtures suitable for direct application or field aplication generally contemplate those in which the active compound ispresent in an amount substantially between about 0.0005 and 20%,preferably 0.1 and 5%, by weight of the mixture. Thus, the presentinvention contemplates over-all compositions which comprise mixtures ofa dispersible carrier vehicle such as a dispersible carrier solid, or adispersible carrier liquid preferably including a carrier vehicleassistant such as an emulsifying agent and/or a dispersing agent, and anamount of the active compound which is effective "for the purpose inquestion and which-is generally between about 0.0005 and 95% by weightof the mixture. Specifically, since the instant active compounds havealso systemic properties, they need not be applied to agricultural cropsby introduction into the vicinal soil of such crops for take-up by theparticular plants, but instead may also be used aboveground by merelyapplying the same alone or in admixture with the carrier vehicle to theplant crops.

In particular, the present invention contemplates methids of selectivelycontrolling or combating anthropods, i.e., insects and acarids, and moreparticularly, methods of combating at least one of insects and acaridswhich comprises applying to at least one of correspondingly (a) suchinsects, (b) such acarids, and (c) the corresponding habitat, acorrespondingly combative amount, i.e., an arthropodically, especiallyinsecticidally or acaricidally, effective amount, of the particularactive compound of the invention alone or together with a carriervehicle as noted above. The instant formulations or compositions areapplied in the usual manner, for instance by spraying, atomizing,vaporizing, scattering, dusting, watering, sprinkling, and the like,whereby to apply the active compounds either to the plant partsthemselves or to the vicinal soil itself, or both.

The following examples are given for the purpose of illustrating, whilenot limiting, the methods of use in accordance with the presentinvention:

EXAMPLE 1 Plutella test Solvent: 3 parts by weight dimethyl formamideEmulsifier: 1 part by weight alkylaryl polyglycol ether.

To produce a suitable preparation of the particular active compound, 1part by weight of such active compound is mixed with' the stated amountof solvent containing the stated amount of emulsifier, and the resultingconcentrate is diluted with Water to the desired final concentration.

Cabbage leaves (Brassica oleracea) are sprayed with the preparation ofthe given active compound until dew moist and infested with thecaterpillars of the diamond back moth (Plutalla maculipennis).-

After thespecified period'of time, the degree of-destructionistdeterrnined pereentagewise. .100% indicates that all of thecaterpillars are killed, whereas 0% indicates that none of them iskilled.

6 The active compounds, their concentrations; theeval pound'so that thepreparation penetrates into the soil uation timeand the results obtainedcan be seen from withoutwetting the leaves of the oat plants. Theparticuthe following Table 1:

TABLE 1.-PLANT DAMAGING INSECTS Concentra- Degree of 1 A tion ofDestruction Active in percent v Compound after4 Active Compound inpercent days CH0, v '0 2 90 I Z t V. 2, 1 0 02 0 h I CQ iflcHslz CHWHM I(Known) C613 0.2 100 H r e a 0. 02 100 (III) F'-CH2CONHCHO-OON(CH3)Z/ 0.002 90 a 1 0.0002 0 0013 0.2 100 0.02 90 (IV) FCHzCONH-CH-OCO-NH- -CH H0.002.. 0 0013 a 0.2 100 1 0.02 (v FCHz-CO-NH-CHO-CO-NH N02 C013 0 V r0.2 100 I 0. 02 30 (v1) F-CHz-CO-NHCHOCO-NH EXAMPLE 2 lar activecompound is taken up by the cat plants from the soil and thus reachesthe infested leaves.

7 After the specified period of time, the degree of desolvent! 3 Parts yWeight dimethyl formamlde struction is determined percentagewise. 100%indicates Emulsifiefi 1 P y Weight alkylaryl P y y Ethel that all of theaphids are killed, whereas 0% indicates To produce a suitablepreparation 'bf'the' particular that none of them is killedactivecompounds, 1 part by weight of such active com- The active compounds,their concentrations, the evalpound i mix d with th t t d o nt of. l t

uation time and the results obtained can. be seen from the taining thestated amount of emulsifier, and the result- 40 following Table 2:

Rhopalosiphum test (systemic action) TABLE 2.PLANI DAMAGING INSECTSConcentra- Degree of tion of Destruction Active in percent Compoundafter 8 Active Compound in percent davs isy --o-00-NH-om 0.02

(Know M 7 C013 0.02 100 (l: y 0.002 100 (III) F-CHz'CONH-- H--O--OON(OH)2 0.0002 80 p i 000002 0 c013 0.02 100 m 0.002 100 IV' Ilif-QHCO-NlL-CH-O-C-O-NHOH3 0.0002 0 GU13 r r 0.2 100 r 1 H (3C1; e 0.2 100(VI') F-CHz.C0-NH-OHOCO'-NHI r 0.002 0 in'g"concei1trateis diluted'withwater to messag s I EXAMPLE 3 concentratiod a 1 Oat plants Ay'enasatiiut) which haveibcen strongly 1 Tetmnychus test infested with .oataphids (Rhopalosiphum p'adi) Qare Solvent: 3 parts by weight dimethylformamide watered with the preparation of the given active com-Emulsifier: "1 part by weight alky l ajryl polyglycol ether. I

concentrate is diluted with water to the desired final concentration.

Bush beans (Phaseolus vulgaris), which have a height of approximately10-30 cm., are sprayed with the preparation of the given active compounduntil dripping Wet. The bush beans are heavily infested with spidermites (Tetranychus telariu's) in all stages of development.

After the specified period of time, the eifectiveness of the preparationof the particular active compound is determined by counting the deadmites. The degree of destruction thus obtained is expressedpercentagewise: 100% indicates that all of the spider mites are killed,whereas indicates that none of them is killed.

The active compounds, their concentrations, the evaluation time and theresults obtained can be seen from 8 C. Yield 10 g. (1.1%-of theory):l-(l-fiuoroacetamido- 2,2,2-trichloro)ethy1-N,N-dimethyl carbamate. 1

EXAMPLE 6 E) l FoHiooNHr JH0-oNH-@o1 67 g. mol) ofchloral-fiuoroacetamide are slurried in 100 cc. of methylene chlorideand mixed at room temperature with 57 g. mol) of 3,4-dichlorophenylisocyanate dissolved in 50 cc. of methylene chloride. Part of thereaction product dissolves butit soon precipitates again. The mixtureisstirred for 10 hours and then suc; tion-filtered. The reaction productis a white crystalline compound melting at 260 C. (decomposition). Yield40 g. (32% of theory): 1-(1-fiuoroacetamido-2,2,Z-trichlothe followingTable 3: ro)ethyl-N-(3,4'-dichlorophenyl)carbamate;'

TABLE 3.-PLANT DAMAGING INSECTS Concentra- 'Degree of tion ofDestruction Active in percent Compound afterg Active Compound inpercentdays (B) (|)CONHOH 0.2 0

(Known) C C]; 0. 2 100 0. 02 0 (III!) F-CHO O-NHOHOC O-N(CH3)2 0. 02 0(IV) F-CHr-C ONHCHOC O-NH--CH3 0 C1 0. 2 100 l 0. 02 10 W1" F-CHz-CONHGH--O-C O-NHQ The production of the particular carbamic acid estersEXAMPLE 7 usable according to the present invention is described in thefollowing typical examples;

EXAMPLE 4 l 112 grams 0/: mol) of chloral-fiuoroacetamide are slurriedin 150 cc. of methylene chloride and mixedat room temperature with g. ofmethyl isocyanate. The chloralfiuoroacetamide dissolves after a fewhours and the corresponding carbamic acid ester is precipitated after afew further hours. Another 30 g. of methyl isocyanate are added tocomplete the reaction. The precipitated product, i.e.1-(1-fiuoroacetamido-2,2,2-trichloro)ethy1 N-methyl carbamate, isfiltered ofl. with suction and recrystallized from methylene chloride.M.P. 133 C. Yield 52 g. (37% of theory).

EXAMPLE 5 0 CH3 l| N Q QTN 001; CH; II)

67 grams mol) of chloral-fluoroacetamide are dissolved. in 200 cc. ofether. 2,4,grams )5 mol) of pyridine-..

are added and then 32 g. mol) of dimethyl-carbamic acid chloride areadded dropwise at 1520 C. The reaction mixture is stirred at roomtemperature for 12 hours and filtered OH with suction from theprecipitated pyridine hydrochloride. The solvent is removed in a vacuum.There remains an oil which slowly crystallizes. M.P. 105

, acetamide and methylene chloride, and each of the followingisocyanates, respectively, in accordance with the procedure of Example4, and each of the following carbamic acid chlorides, respectively, inaccordance with the pre edurc of Examp e (a) tert.-butyl-isocyanate;

(b) N-see.-butyl-N-(4-isopropoxy)-n-butyl-carbamic acid chloride; Mn.

(c) N-methoxy-methyl-Ni2-chloro)ethyl-carbamic acid chloride; r (d)N-(Z-iso-butoxy)-ethyl-N-(3-nitro)m-propylcarbamic acid'chloride; p (e)N- (2-chloro-2-fluoro -n-propyl-N- (3-chloro-4-ethoxy-S-nitro)-phenyl-carbamic acid chloride;

9 (f) N- (2-bromo -ethyl-N- 3-cyano -n-propyl-car-bamic acid chloride;and p (g) N-(3-bromo-4-fluoro) nbutyl-isocyanate, t

the corresponding 1 (l-fluoroacetamido-2,2,Z-trichloro)-ethyl-carbamates are produced: 7 1

Advantageously, in accordance with the present invention, in theforegoing formulae:

R represents hydrogen; or alkyl having 1-4 carbon atoms, such as methyl,ethyl, n-propyl, isopropyl, n-butyl, iso butyl, sec.-butyl, tert.-butyl,and the like, i.e., lower alkyl, which may be unsubstituted or mono,di-, or polysubstituted with alkoxy having l4 carbon atoms, such asmethoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, isobutoxy,sec.-butoxy, tert.-butoxy, and the like, i.e., lower alkoxy, andespecially alkoxy having 1-2 carbon atoms, or halo, such as chloro,bromo, fluoro, and iodo, and especially chloro, fluoro and/or bromo aswell as mixed alkoxy and halo substituents of the foregoing type; and

R represents alkyl having 1-4 carbon atoms, such as the radicalsmentioned in the immediately preceding paragraph for R; or phenyl, whichalkyl or phenyl may be unsubstituted or mono-, dior poly-substitutedwith alkoxy having 1-4 carbon atoms, such as the radicals mentioned inthe immediately preceding paragraph for the alkoxy substituents,especially alkoxy having 1-2 carbon atoms, i.e., methoxy or ethoxy, orhalo, such as chloro, bromo, fluoro, and iodo, and especially chloro,fiuoro and/or bromo, or nitro, or cyano, as Well as mixed alkoxy, halo,nitro and cyano substituents of the aforementioned type.

In particular, preferred esters coming within the purview of the presentinvention include l-(l-fluoroacetamido 2,2,2 trichloro) ethyl N (C -Calkyl)- carbamate having the formula FCH -C--NH--CHO-GNH-(C -C4 alkyl) 1(1 fluoro acetamido 2,2,2 trichloro) ethyl N, N-di(C -C aIkyD-carbamatehaving the formula:

and 1 (l fluoroacetamido 2,2,2 trichloro) ethyl- N-phenyl-carbamatehaving the formula:

0 C01 0 (Z)n in which Z is selected from the group consisting of alkoxyhaving 1-4 carbon atoms, chloro, and nitro, and n is a number from 0 to2.

It will be realized by the artisan that all of the foregoing estercompounds contemplated by the present invention possess the desiredselective arthropodicidal, i.e., insecticidal or acaricidal, propertiesfor combating insects and acarids, and that such compounds have not onlya very slight toxicity toward warm-blooded creatures, ex-

cept selectively rodents, such as short-tailed mice, as may be seen fromthe aforesaid copending US. application Ser. No. 499,068, but also a lowphyto'toxicity. It will 'be appreciated that.as used herein, i.e., bothin the specification and claims, the terms arthropod, arthropodicidaland arthropodicide are defined as including specifically both insectsand acarids within the contemplation of their meaning, for conveniencein determining the collective aspects of utility herein. Thus, theinsects and acarids may be considered herein collectively as arthropodsto be combated collectively in accordance with the invention, andaccordingly the insecticidal and/or acaricidal activity may be termedarthropodicidal activity, and the concomitant combative or effectiveamount used in accordance with the invention will be anarthropodicidally effective amount which in efiect means aninsecticidally or acaricidally effective amount of the active compoundfor the desired purposes. It will be appreciated that the instant:specification and examples are set forth by way of illustration and notlimitation, and that various modifications and changes may be madewithout departing from the spirit and scope of the present inventionwhich is to be limited only by the scope of the appended claims.

What is claimed is: ,1. Method of killing insects and acarids whichcomprises applying to at least one of (a) such insects, (b) suchacarids, and (c) the corresponding habitat thereof, an effective amountof a l-(l-fluoroacetamido-2,2,2-trichloro)ethyl carbamate having theformula 0 C 013 (l'l) in which R represents a member selected from thegroup consisting of hydrogen, alkyl having 14 carbon atoms, andsubstituted alkyl having 1-4 carbon atoms which is substituted with amember selected from the group consisting of alkoxy having 1-4 carbonatoms, halo, and mixtures of such substituents, and R represents amember selected from the group consisting of alkyl having 1-4 carbonatoms, phenyl, and the corresponding substituted alkyl and phenyl whichare substituted with a member selected from the group consisting ofalkoxy having 1-4 carbon atoms, halo, nitro, cyano, and mixtures of suchsubstituents.

2. Method according to claim 1 wherein said carbamate is used in theform of a mixture with a dispersible carrier vehicle, with saidcarbamate being present in an amount substantially between about 00005and by weight of the mixture.

3. Method according to claim 1 wherein said carbamate is applied toagricultural soil.

4. Method according to claim 1 wherein said carbamate is 1-(1fluoroacetamido-2,2,2-trichloro)ethyl-N- (C -C alkyl)-carbamate havingthe formula mate is 1-(1 fiuoroacetamido-2,2,2-trichloro)ethyl-N, N-di(C-C alkyl)-carbamate having the formula (C 1-C4 alkyl) 6. Methodaccording to claim 1 wherein said 'carbamate is 1-(1fluoroacetamido-Z,2,2-trichloro)ethyl-N- phenyl carbamate having theformula CH3 8. Method according to claim 1 wherein said carbamate is1-(1 fiuoroacetamido-2,2,2-trich1oro)ethyl-N- methyl carbamate havingthe formula 9 C013 (H) FOIh-O-NH-CEP-O-O-NH-OH;

9. Method according to claim 1 wherein said carbamate is 1-(1fluoroacetamido-2,2,2-trichloro)ethyl-N- (4-nitropheny1)-carbamatehaving the formula 10. Method according to claim 1 wherein saidcarbamate is 1-(1 fluoroacetamido-2,2,2-trichloro)ethyl-N-phenyl-carbamate having the formula 1 2 7 11. Method according to claim1 wherein said carbamate is 1-(1fiuoroacetamido-2,2,2-trich1oro)ethyl-N- (4-ethoxy-phenyl)-carbamatehaving the formula 12. Method according to claim 1 wherein saidcarbamate is 1-(1-fluoroacetarnido-2,2,2-trichloro)ethyl-N-(3,4'-dichlorophenyl)-carbamate having the formula f!) C 013 O l ReferencesCited UNITED STATES PATENTS 2,273,849 '2/1942 "Epstein et al. 16722 2,49,340 5/1949 Payne 16722 3,211,770 10/1965 Pyne 16722 3,234,248 2/1966Scherer et a1. 167-22 3,253,030 5/1966 Buc 16722 OTHER REFERENCES Piankaet a1., N-Substituted methylarnides, (1965) Brit. 993,051, May 26, 1965,CA 63, p. 9822 (1965).

LEWIS 'GOTTS, Primary Examiner G. HOVL'LRAH, Assistant Examiner-U.s.'c1. X.R.

3 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,475,490 Dated Nov 4,1969

Inventor(s) CHRISTA ST. and msmaoas m It is certified that error appearsin the above-identified patent and that said Letters Patent are herebycorrected as shown below:

T- Column 3, line 1 (specification, page a, line 11) "hesperdium" shouldbe --hesperidum-'-; column 4, line 19 I (specification, page 7, line 14)"0.1" should be' 0.01"; c'olumnfi, line 36 (specification, page 8, line2) "ids" should be --ods--; column 4, line 42 (specification, page 8line 7) "arthropodically" should be -srthropodicidally column 5, Table 1(specification, page 9, line 15) under the heading "Concentration ofActive Compound in percent" '0 2" the first figure in the verticalcolumn should be --0.2-; column 6, Table 2 (specification, page 11,lines 5-6) under the heading "Degree of Destruction in percent after 8days" for the first vertical entry insert the figure "6-- SIGNED AN'DSEALED JUN 3 01970 Anon:

Edward Mmmhmk mm E! mmg, .m. testing 0mm missions! of Patents

